This invention relates to the production of oxygen-containing organic products from the reaction of oxides of carbon and hydrogen in the presence of a cobalt-containing catalyst of the formula EQU Co.sub.3 (CO).sub.9 C--Y
wherein Y is as hereinafter described.
Owing to the limited availability of petroleum sources the cost of producing chemicals from petroleum has been steadily increasing and many have raised the dire prediction of significant oil shortages in the future. Obviously, a different low cost source is needed which can be converted into the valuable chemicals now derived from petroleum sources. Synthesis gas* is one such source which can be effectively utilized in certain circumstances to make chemicals. FNT *For the purposes of the discussion and descriptions contained herein, mixtures of hydrogen and carbon monoxide, regardless of the amount of each present, will be characterized, for the sake of convenience, as "synthesis gas".
The most desirable aspect of synthesis gas is that it can be produced from non-petroleum sources. Synthesis gas may be derived by the combustion of any carbonaceous material including coal, or any organic material, such as hydrocarbons, carbohydrates and the like. Synthesis gas has for a long time been considered a desirable starting material for the manufacture of a variety of chemicals. A number of chemicals have been made commercially from synthesis gas. Hydrocarbons have been made by the Fischer-Tropsch catalytic reaction. Methanol is commercially manufactured by a heterogeneous catalytic reaction from synthesis gas. Aldehydes and alcohols are made from the reaction of olefins and synthesis gas. If one could expand the production of chemicals in a commercial manner from synthesis gas then one would not be as dependent upon petroleum as the basic raw material even though it is an excellent raw material for making synthesis gas. Accordingly, intense interest in such processes has developed.
Pruett and Walker, U.S. Pat. No. 3,833,634, patented Sept. 3, 1974, describes a process for preparing glycols by reacting an oxide of carbon with hydrogen using a rhodium carbonyl complex catalyst. The examples of the patent compare the reaction of hydrogen and carbon monoxide in the presence of the desired rhodium containing catalyst and other metals. In Example 17 of the patent, the reaction was attempted with dicobalt octacarbonyl as the catalyst using acetic acid as the solvent with a reaction temperature of 230.degree. C., for 2 hours, and "the product contained no polyhydric alchol," but traces of the mono-and diacetate of ethylene glycol were detected.
Gresham, U.S. Pat. No. 2,535,060, describes a process for preparing monohydric alcohols by introducing carbon monoxide, hydrogen and a hydroxylated solvent into a reaction vessel and heating the mixture in the presence of a ruthenium-containing substance and an alkaline reagent which controls the pH within the range of 7 to 11.5, at a temperature within the range of 150.degree. to 300.degree. C. under a pressure within the range of 200 to 1,000 atmospheres.
U.S. Pat. No. 2,636,046, filed Oct. 16, 1948, to Gresham describes the production of polyfunctional oxygen-containing organic products including such compounds as ethylene glycol, glycerine, and the like.* This is accomplished by the reaction of hydrogen with carbon monoxide in the presence of a solvent to produce glycol. According to this patent, the reaction of carbon monoxide with hydrogen must be at pressures of above 1,000 atmospheres and "particularly above a minimum of about 1,400 atmospheres" in order to obtain the "polyfunctional oxygen-containing organic compounds . . . in excellent yield" (column 2, lines 9-17).
The patent specifically states at column 2, lines 37-43, that:
"[I]n the hydrogenation of oxides of carbon at pressures of 1,000 atmospheres and below, virtually no polyfunctional compounds are produced. At pressures above 1,000 atmospheres and especially at pressures of about 1,500 to 5,000 atmospheres, preferably 2,000 to 5,000 atmospheres, polyfunctional compounds are obtained."
The examples of the U.S. Pat. No. 2,636,046 describe the use of a cobalt catalyst; the patentee, at column 3, line 61, indicates that the catalyst may contain "cobalt, ruthenium, etc." FNT *Note the evaluation of this work by Rathke and Feder, JACS, 100, pp. 3623-3625 (May 24, 1978).
According to Roy L. Pruett, Annals, New York Academy of Sciences, Vol. 295, pages 239-248 (1977), at page 245, metals other than rhodium were tested to determine the production of ethylene glycol from mixtures of carbon monoxide and hydrogen. These metals include cobalt, ruthenium, copper, manganese, iridium and platinum. Of these metals, cobalt was found to have a slight activity, citing British Pat. No. 665,698 which corresponds generally to the last mentioned Gresham U.S. Patent. Pruett stated that such slight activity with cobalt was "qualitatively" in agreement with the results obtained by Ziesecke, 1952, Brennstoff-chem, 33:385.
The production of acetaldehyde from methanol, hydrogen and carbon monoxide in the presence of a cobalt catalyst is disclosed in U.S. Pat. No. 4,151,2098. Similarly, Japanese Publication Nos. JA77/13611 discloses a process catalyzed by cobalt, a halogen, and phosphorus.
The existence of substituted methinyl tris (tricarbonylcobalt) complexes is disclosed in "Novel Carbonylation Reaction of Substituted Methinyl Tris (Tricarbonyl Cobalt) Complexes", K. Tominaga., et al., Tetrahedron Letters, No. 25, 2217-2220 (1970). The complexes disclosed therein are of the general formula YC--Co.sub.3 (CO).sub.9 where Y represents hydrogen, alkyl, aryl, halogen, --COOH, --COOR, --CH.sub.2 CH.sub.2 COOH, --CH.dbd.CHCOOH, etc. The complexes are employed in a dicarbonylation reaction on the same carbon atom with the metal carbonyl. The reaction employs an organic base and a cobalt-containing catalyst in an alcohol solvent under a carbon monoxide pressure with the exception that methanolysis of CH.sub.3 --C--Co.sub.3 (CO).sub.9 under hydrogen pressure and hydrogenolysis of CH.sub.3 --C--Co.sub.3 (CO).sub.9 under a pressure of hydrogen and carbon monoxide are reported. The methanolysis of CH.sub.3 --C--Co.sub.3 (CO).sub.9 (hydrogen pressure 100 atm) gave 36 percent (basis not reported) methyl propionate, 64 percent 1,1-dimethyoxypropane with a molar ratio of 16:84 respectively. The hydrogenolysis of CH.sub. 3 --C--Co.sub.3 (CO).sub.9 in benzene solution in the presence of hydrogen and carbon monoxide gave a yield of 50 percent (basis not reported) propionaldehyde. It is not clear from the disclosure as to whether an organic baase was employed in the methanolysis and hydrogenolysis reactions.
Recently, the formation of the tricobalt carbonyl anionic cluster [Co.sub.3 (CO).sub.10 ].sup.- was reported by G. Fachinetti, J.C.S., Chem. Comm., 396-397 (1979). The molecular structure of LiCo.sub.3 (CO).sub.10 --i--Pr.sub.2 O has been reported by Hans-Norbert Adams, et al., Angew. Chem. Vol. 19, 404-405 (1980).
The preparation and characterization of the acid Co.sub.3 (CO.sub.9 C--OH has been reported by G. Fachinetti, J.C.S., Chem. Comm., 397-398 (1978). The crystal and molecular structure of this acid has been discussed by Hans-Norbert Adams, Angew. Chem. Int. Ed., 20, 125-126 (1981). The author, at page 126, suggested the acid Co.sub.3 (CO).sub.9 C--OH as a model for the homogeneous phase hydrogenation of CO to methanol (citing G. L. Geoffroy and R. A. Epstein, Inorg. Chem. 16, 2795 (1977) and E. L. Muetterties, J. Stein, Chem. Rev., 79, 479 (1979) on the hydrogenation of Co.sub.3 (CO).sub.9 C--R to hydrocarbons as additional basis for this suggestion.
The formation of HCo.sub.3 (CO).sub.9 by the loss of carbon monoxide by the acid Co.sub.3 (CO).sub.9 C--OH has been reported by G. Fachinetti, et al., Angew. Chem., Vol. 18, 619-620 (1979). Further, the latter report shows the formation of Co.sub.3 (CO).sub.9 C--CH.sub.3 by the reaction of HCo.sub.3 (CO).sub.9 and acetylene. The formation and isolation of HCo.sub.3 (CO).sub.9 is discussed further by G. Fachinetti, Angew. Chem. Int. Ed., 20, 204-206 (1981). In addition, the latter reports the preparations of the triethylamine adduct of Co.sub.3 (CO).sub.9 C--OH and the triethylamine adduct of HCo(CO).sub.4 is reported by F. Calderazzo, J.C.S. Chem. Comm., 183-188 (1981).